Production of Olefin Polymerization Catalysts

ABSTRACT

The invention provides a process for producing an olefin polymerisation catalyst, comprising an organometallic compound of a transition metal or of an actinide or lanthanide, in the form of solid catalyst particles, comprising forming a liquid/liquid emulsion system which comprises a solution of one or more catalyst components dispersed in a solvent immiscible therewith; and solidifying said dispersed phase to convert said droplets to solid particles comprising the catalyst and optionally recovering said particles.

This invention relates to a process for the production of catalysts forolefin polymerisation, and to their use in polymerising olefins.

BACKGROUND ART

Catalyst systems which are solutions of one or more catalyst components(e.g. a transition metal compound and optionally a cocatalyst) are knownin the filed as homogeneous catalyst systems. Homogeneous systems areused as liquids in the polymerisation process. Such systems have ingeneral a satisfactory catalytic activity, but their problem has beenthat the polymer thus produced has a poor morphology (e.g. the endpolymer is in a form of a fluff having a low bulk density). As aconsequence, operation of slurry and gas phase reactors using ahomogeneous catalyst system cause problems in practice as i.a. foulingof the reactor can occur.

The above problems have been tried to overcome in several ways: Thehomogeneous system has been prepolymerised with an olefin monomer beforethe actual polymerisation step. Said prepolymerisation, however, has notsolved the problem of the formation of a polymer fluff. EP 426 646 ofFina has further suggested to use specific prepolymerisation conditions,i.e. the reaction temperature and the reaction time of a narrow,specific range, for improving the morphology of the polymer thusobtained.

In WO 98 37103 the homogeneous catalyst system is introduced as dropletsof a certain size into the polymerisation reactor for controlling theaverage particle size of a polyolefin produced in gas phasepolymerisation. Said droplets are formed just before the introduction byusing an atomizer (e.g. a spray nozzle).

Furthermore, to overcome the problems of the homogeneous systems in anon-solution process the catalyst components have been supported, e.g.their solution impregnated, on porous organic or inorganic supportmaterial, e.g. silica. These supported systems, known as heterogeneouscatalyst systems, can additionally be prepolymerised in order to furtherimmobilise and stabilise the catalyst components.

However, also supported and optionally prepolymerised systems presentproblems. It is difficult to get an even distribution of the catalystcomponents in the porous carrier material; and leaching of the catalystcomponents from the support can occur. Such drawbacks lead to anunsatisfactory polymerisation behaviour of the catalyst, and as a resultthe morphology of the polymer product thus obtained is also poor.Furthermore, the uneven distribution of the catalyst components in thesupport material can have an adverse influence on the fragmentation ofthe support material during the polymerisation step.

The support can also have an adverse effect on the activity of thecatalyst, on its polymerisation behaviour and on the properties of theend polymer.

Accordingly, various measures have been proposed to improve themorphology properties of homogeneous catalyst systems. However, due tothe complexity of the catalyst systems, the need still exists to developfurther catalyst systems and preparation methods thereof which overcomethe problems of the prior art practice.

SUMMARY OF THE INVENTION

The present invention provides a further method for preparing a solidcatalyst for polyolefin polymerisation.

Another object of the invention is to provide an alternative method forproducing solid spherical particles without supporting catalystcomponents to a porous support.

A further object is to provide a polymerisation process using thecatalyst prepared according to the method of the invention, as well as acatalyst obtainable by the method of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the particle size distribution of catalyst particlesaccording to the invention prepared in Example 1.

FIG. 2 illustrates the nearly perfect spherical shape of catalystparticles according to the invention prepared in Example 1.

FIG. 3 shows the particle size distribution of catalyst particlesaccording to the invention prepared in Example 5.

DESCRIPTION OF THE INVENTION

The invention is based on the finding that a homogeneous catalyst systemcontaining an organometallic compound of a transition metal can beconverted, in a controlled way, to solid, uniform catalyst particles byfirst forming a liquid/liquid emulsion system, which comprises as thedispersed phase, said solution of the homogeneous catalyst system, andas the continuous phase a solvent immiscible therewith, and thensolidifying said dispersed droplets to form solid particles comprisingthe said catalyst.

The made invention enables for the first time to obtain solid sphericalcatalyst particles of said organotransition metal catalyst without usinge.g. external porous carrier particles, such as silica, normallyrequired in the prior art.

An uniform distribution of the chemical composition, both intra- andinterparticles, can thus be obtained. Advantageously, the catalystparticles of the invention have a uniform catalytical behaviour in apolymerisation process. E.g. the catalyst can provide a uniform start-upof the polymerisation in a polymerisation process.

More specifically, the present invention provides a method for producingan olefin polymerisation catalyst, comprising an organometallic compoundof a transition metal, in the form of solid catalyst particles,comprising

preparing a solution of one or more catalyst components;

dispersing said solution in a solvent immiscible therewith to form anemulsion in which said one or more catalyst components are present inthe droplets of the dispersed phase;

immobilising the catalyst components in the dispersed droplets, in theabsence of an external particulate porous support, to form solidparticles comprising the said catalyst, and optionally recovering saidparticles.

By the term “preparing a solution of one or more catalyst components” isnaturally meant that the catalyst forming compounds may be combined inone solution which is dispersed to the immiscible solvent, or,alternatively, at least two separate catalyst solutions for each or partof the catalyst forming compounds may be prepared, which are thendispersed successively to the immiscible solvent.

In a preferable embodiment of the invention a solution of one or morecatalyst components, comprising said transition metal compound andoptionally a cocatalyst(s), is combined with an inert solvent immiscibletherewith to form an emulsion wherein that solvent forms the continuousliquid phase and the solution comprising the catalyst component(s) isdispersed in the form of droplets (discontinuous phase). The dropletsare then solidified to form solid catalyst particles, and the solidparticles are separated from the liquid and optionally washed and/ordried.

The terms “immobilisation” and “solidification” are used hereininterchangeably for the same purpose, i.e. for forming free flowingsolid catalyst particles in the absence an external porous particulatecarrier, such as silica. Said step can thus be effected in various ways:(i) by effecting a prepolymerisation reaction within the said droplets,(ii) by cross-linking, e.g. fully or partially cross-linking a catalystcomponent within the said droplets by adding cross-linking agent, (iii)by effecting a chemical reaction within the droplets whereby thereaction product precipitates (“solidifies”), and/or (iv) by causing anexternal stimulus to the emulsion system such as a temperature change tocause the solidification. Thus in said step the catalyst component(s)remain “fixed” within the formed solid particles. It is also possiblethat one or more of the catalyst components may take part in thesolidification/immobilisation reaction.

Accordingly, solid, compositionally uniform particles having apredetermined particle size range are obtained.

Furthermore, the particle size of the catalyst particles of theinvention can be controlled by the size of the droplets in the solution,and spherical particles with an uniform particle size distribution canbe obtained.

The invention is also industrially advantageous, since it enables thepreparation of the solid particles to be carried out as a one-potprocedure.

Dispersed Phase

The principles for preparing two phase emulsion systems are known in thechemical field. Thus, in order to form the two phase liquid system, thesolution of the catalyst component(s) and the solvent used as thecontinuous liquid phase have to be essentially immiscible at leastduring the dispersing step. This can be achieved in a known manner e.g.by choosing said two liquids and/or the temperature of the dispersingstep/solidifying step accordingly.

A solvent may be employed to form the solution of the catalystcomponent(s). Said solvent is chosen so that it dissolves said catalystcomponent(s). The solvent can be preferably an organic solvent such asused in the field, comprising an optionally substituted hydrocarbon suchas linear or branched aliphatic, alicyclic or aromatic hydrocarbon, suchas a linear or cyclic alkane or alkene, an aromatic hydrocarbon and/or ahalogen containing hydrocarbon. Examples of aromatic hydrocarbons aretoluene, benzene, ethylbenzene, propylbenzene, butylbenzene and xylene.Toluene is a preferred solvent. The solution may comprise one or moresolvents. Such an inert solvent can thus be used to facilitate theemulsion formation, and usually does not form part of the solidifiedparticles, but e.g. is removed after the solidification step togetherwith the continuous phase.

Alternatively, a solvent may take part to the solidification, e.g. aninert hydrocarbon having a high melting point (waxes), such as above 40°C., suitably above 70° C., e.g. above 80° C. or 90° C., may be used assolvents of the dispersed phase to immobilise the catalyst compoundswithin the formed droplets.

In another embodiment, the solvent consists partly or completely of aliquid monomer, e.g. liquid olefin monomer designed to be polymerised ina “prepolymerisation” immobilisation step.

Continuous Phase

The solvent used to form the continuous liquid phase is a single solventor a mixture of different solvents and is immiscible with the solutionof the catalyst component(s) at least at the conditions (e.g.temperatures) used during the dispersing step. Preferably said solventis inert in relation to said compounds.

The term “inert in relation to said compounds” means herein that thesolvent of the continuous phase is chemically inert, i.e. undergoes nochemical reaction with any catalyst forming component or catalystprecursor forming component. Thus, the solid particles of the catalystor any precursor thereof are formed in the droplets from the compoundswhich originate from the dispersed phase, i.e. are provided to theemulsion in a solution dispersed into the continuous phase.

It is preferred that the catalyst component(s) used for forming thesolid catalyst or catalyst component, as defined under “catalystcompounds” below, will not be soluble in the solvent of the continuousliquid phase. Preferably, said catalyst component(s) are essentiallyinsoluble in said continuous phase forming solvent.

It was the basic finding of the inventors that the solidification takesplace essentially after the droplets are formed, i.e. the solidificationis effected within the droplets e.g. by causing a solidifying reactionamong the compounds present in the droplets. Furthermore, even if somesolidifying agent is added to the system separately, it reacts withinthe droplet phase as no catalyst forming components of the droplets goto the continuous phase to react there.

The term “emulsion” used herein covers both bi- and multiphasic systems.

This finding also applies to cases where the solvent is removed from thedroplets (e.g. due to a temperature change) to cause the solidificationof the active ingredients, whereby said solidifying ingredients remainessentially in a “droplet” form.

In a particularly preferred embodiment of the invention said solventforming the continuous phase is an inert solvent and includeshalogenated organic solvents, particularly fluorinated organic solvents,preferably semi, highly or perfluorinated organic solvents andfunctionalised derivatives thereof, which means that said solvents maycontain other functional groups and/or further halogens such aschlorine.

Examples of the above-mentioned solvents are semi, highly orperfluorinated (a) hydrocarbons, such as alkanes, alkenes andcycloalkanes, (b) ethers, e.g. perfluorinated ethers and (c) amines,particularly tertiary amines, and functionalised derivatives thereof.Preferred are perfluorohydrocarbons of e.g. C3-C30, such as C4-C10.Specific examples of suitable perfluoroalkanes and -cycloalkanes includeperfluorohexane, -heptane, -octane and -(methylcyclohexane). Semifluorinated hydrocarbons relates particularly to semifluorinatedn-alkanes, such as perfluoroalkyl-alkane.

“Semi fluorinated” hydrocarbons also include such hydrocarbons whereinblocks of —C—F and —C—H alternate.

“Highly fluorinated” means that the majority of the —C—H units arereplaced with —C—F units. “Perfluorinated” means that all —C—H units arereplaced with —C—F units. In this respect, it is referred to thearticles of A. Enders and G. Maas in “Chemie in unserer Zeit”, 34.Jahrg. 2000, Nr.6, and of Pierandrea Lo Nostro in “Advances in Colloidand Interface Science, 56 (1995) 245-287, Elsevier Science.

The fluorinated solvents are particularly preferred as they are unpolar,hydrophobic and have very limited miscibility with common organicsolvents in certain temperature ranges.

Furthermore, these fluorinated solvents are chemically very inert andare very poor solvents for polar compounds such as catalytically activecompounds and precursors or reaction products thereof. This finding ofthe inventors is very important in the formation of catalyst particles,because the reactive compounds can be kept within the droplet phase sothat no relevant reactions in the continuous phase occur, which wouldworsen the morphology of the solidified catalyst particles.

Due to the above poor solvent properties, the “droplet form” of thecatalyst components remains even if the solvent used initially in thecatalyst solution is removed during solidification e.g. by heating thesystem.

The present invention is therefore also directed to the use of saidfluorinated organic solvents or mixtures thereof for the preparation ofan at least two-phase emulsion system for producing solid olefinpolymerisation catalysts, wherein said at least two-phase emulsionsystem comprises continuous and dispersed phases and wherein saidfluorinated organic solvent or mixtures thereof form the continuousphase of the emulsion.

Dispersing Step

The emulsion can be formed by any means known in the art: by mixing,such as by stirring said solution vigorously to said solvent forming thecontinuous phase or by means of mixing mills, or by means of ultra sonicwave. The mixing may be effected at lower or elevated temperatures, e.g.between 0 and 100° C., depending i.a. on the used solvents, and ischosen accordingly.

A further possibility is to use a so called phase change method forpreparing the emulsion by first forming a homogeneous system which isthen transferred by changing the temperature of the system to a at leastbiphasic system so that droplets will be formed. If needed, part of thecatalyst forming compounds may be added after the emulsion system isformed.

The emulsion formation via said “one phase” change may be one preferablemethod, especially when e.g. fluorinated solvents are used as thecontinuous phase, since the miscibility of the fluorinated solvents, inparticular perfluorinated solvents, with common organic solvents (e.g.alkane, such as pentane, hexane, chloroform, toluene) is dependent onthe temperature so that a one phase system (homogeneous phase) of thefluorous solvent and a common organic solvent can be formed above acertain critical temperature.

The ratio of the first (e.g. fluorous solvent) and the second solvent(catalyst solution is chosen so that the first solution forms thediscontinuous phase (droplets) in the at least two phase system.

The two phase state is maintained during the emulsion formation step andthe solidification step, as for example, by appropriate stirring.

Additionally, emulsifying agents/emulsion stabilisers can be used,preferably in a manner known in the art, for facilitating the formationand/or stability of the emulsion. For the said purposes, surfactants,e.g. such as surfactants based on hydrocarbons (including polymerichydrocarbons with a molecular weight e.g. up to 10 000, optionallyinterrupted with a heteroatom(s)), preferably halogenated hydrocarbons,such as semi-, or highly-fluorinated hydrocarbons optionally having afunctional group, or, preferably semi-, highly- or perfluorinatedhydrocarbons having a functionalised terminal, can be used.

Alternatively, an emulsifying and/or emulsion stabilising aid can alsobe formed by reacting a surfactant precursor bearing at least onefunctional group with a compound reactive with said functional group andpresent in the catalyst solution or in the solvent forming thecontinuous phase. The obtained reaction product acts as the actualemulsifying aid and/or stabiliser in the formed emulsion system. Thisembodiment is not bound to the present invention, but in principal canbe used for forming any emulsion system, and also for preparingcatalysts other than the present catalysts, e.g. catalysts of ZieglerNatta type.

Examples of the surfactant precursors usable for forming said reactionproduct include e.g. known surfactants which bear at least onefunctional group selected e.g. from —OH, —SH, —NH₂, —COOH, —COONH₂,and/or any reactive derivative of these groups, e.g. semi-, highly orperfluorinated hydrocarbons bearing one or more of said functionalgroups. Preferably, the surfactant precursor has a terminalfunctionality as defined above.

The compound reacting with such surfactant precursor is preferablycontained in the catalyst solution and may be a further additive or oneor more of the catalyst forming compounds, preferably other than thecatalytically active transition metal compound (e.g. other thanmetallocene or non-metallocene). Such compound is preferably e.g. acoactivator, such as a compound of group 13, suitably an organoaluminiumcompound, such as an aluminium alkyl compound optionally comprisinghalogen or, preferably, in case of metallocenes, an aluminoxane compound(e.g. as known in the art).

The addition of the surfactant precursor may be effected e.g. before thedispersing step of the catalyst solution. However, the surfactantprecursor may also be added to the formed emulsion system, whereby,preferably, the transition metal compound, e.g. a metallocene, is addedto the dispersed phase after the formation of the reaction product ofthe surfactant precursor and said compound, e.g. a cocatalyst, of theemulsion system. After said reaction, if needed, the amount of saidcompound, e.g. a cocatalyst, in the catalyst solution may be increasedwith a further addition of the compound, either separately or e.g.together with the transition metal compound.

Preferably, the surfactant precursor is reacted with a compound of thecatalyst solution before the addition of the transition metal compound.In a preferred embodiment a highly fluorinated C₁₋₃₀— (suitably C₄₋₂₀—or C₅₋₁₀—) alcohol (e.g. highly fluorinated heptanol, octanol ornonanol) is reacted with a cocatalyst, in the present inventionpreferably aluminoxane, present in the catalyst solution to form the“actual” surfactant. Then, an additional amount of cocatalyst and thetransition metal compound, e.g. a metallocene, is added to said solutionand the obtained solution is dispersed to the solvent forming thecontinuous phase. The “actual” surfactant solution may be preparedbefore the dispersing step or in the dispersed system. If said solutionis made before the dispersing step, then the prepared “actual”surfactant solution and the transition metal solution may be dispersedsuccessively (e.g. the surfactant solution first) to the immisciblesolvent, or be combined together before the dispersing step.

The droplet size and size distribution of the formed discontinuous phasecan be selected or controlled in a manner known in the art, i.a. by thechoice of the device for emulsion formation and by the energy put intoemulsification.

In the preparation process of the invention, the solution may alreadycontain all the compounds (to be added) before the dispersing stepthereof. Alternatively, e.g. depending on the reactivity of thecompounds, the dispersed phase can be formed first from one or more ofthe compounds and, thereafter, the other compound(s) can be addedseparately to said dispersed phase. Said other compounds can be added ina form of a solution or already in a form of an emulsion. Portion-wiseadditions of the dispersed phase are also possible.

Additional agents and/or components can be added to the system in anystage of the dispersing and/or solidification step, if needed.

Catalyst Compounds

The term “catalyst component” as used herein includes, in addition tosaid transition metal compound, also any additional cocatalyst(s) (e.g.additional transition metal compounds and/or activators and/or poisonscavengers) and/or any reaction product(s) of a transition compound(s)and a cocatalyst(s). Thus the catalyst may be formed in situ from thecatalyst components in said solution in a manner known in the art.

It should also be understood that the catalyst prepared according to theinvention may be used as such in the polymerisation process or mayrepresent a “catalyst precursor” which is further activated or treatedto form the active catalyst system. Furthermore, said catalyst of theinvention may be part of a further catalyst system. These alternativesare within the knowledge of a skilled person.

The term “an organometallic compound of a transition metal” includes anymetallocene or non-metallocene compound of a transition metal whichbears at least one organic (coordination) ligand and exhibits thecatalytic activity alone or together with a cocatalyst. The transitionmetal compounds are well known in the art and the present inventioncovers e.g. compounds of metals from Group 3 to 10, e.g. Group 3 to 7,or 3 to 6, such as Group 4 to 6 of the Periodic Table, (IUPAC,Nomenclature of Inorganic Chemistry, 1989), as well as lanthanides oractinides.

Accordingly, said organotransition metal compound may have the followingformula I:(L)_(m)R_(n)MX_(q)  (I)wherein M is a transition metal as defined above and each X isindependently a monovalent anionic ligand, such as a σ-ligand, each L isindependently an organic ligand which coordinates to M, R is a bridginggroup linking two ligands L, m is 1, 2 or 3, n is 0, 1 or 2, preferably0 or 1, q is 1, 2 or 3, and m+q is equal to the valency of the metal.

In a more preferred definition, each L is independently (a) asubstituted or unsubstituted cyclopentadiene or a mono-, bi- ormultifused derivative of a cyclopentadiene which optionally bear furthersubstituents and/or one or more hetero ring atoms from a Group 13 to 16of the Periodic Table (IUPAC); or (b) an acyclic, η¹- to η⁴ or η⁶-ligandcomposed of atoms from Groups 13 to 16 of the Periodic Table, and inwhich the open chain ligand may be fused with one or two, preferablytwo, aromatic or non-aromatic rings and/or bear further substituents; or(c) a cyclic σ-, η¹- to η⁴- or η⁶, mono-, bi- or multidentate ligandcomposed of unsubstituted or substituted mono-, bi- or multicyclic ringsystems selected from aromatic or non-aromatic or partially saturatedring systems, and containing carbon ring atoms and optionally one ormore heteroatoms selected from Groups 15 and 16 of the Periodic Table.

By “σ-ligand” is meant a group bonded to the metal at one or more placesvia a sigma bond.

According to a preferred embodiment said organotransition metal compoundI is a group of compounds known as metallocenes. Said metallocenes bearat least one organic ligand, generally 1, 2 or 3, e.g. 1 or 2, which isη-bonded to the metal, e.g. a η²⁻⁶-ligand, such as a η⁵-ligand.Preferably, a metallocene is a Group 4 to 6 transition metal, suitablytitanocene, zirconocene or hafnocene, which contains at least oneη⁵-ligand, which is e.g. an optionally substituted cyclopentadienyl, anoptionally substituted indenyl, an optionally substitutedtetrahydroindenyl or an optionally substituted fluorenyl.

The metallocene compound may have a formula II:(Cp)_(m)R_(n)MX_(q)  (II)wherein:

each Cp independently is an unsubstituted or substituted and/or fusedhomo- or heterocyclopentadienyl ligand, e.g. substituted orunsubstituted cyclopentadienyl, substituted or unsubstituted indenyl orsubstituted or unsubstituted fluorenyl ligand; the optional one or moresubstituent(s) being selected preferably from halogen, hydrocarbyl (e.g.C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl,C6-C20-aryl or C7-C20-arylalkyl), C3-C12-cycloalkyl which contains 1, 2,3 or 4 heteroatom(s) in the ring moiety, C6-C20-heteroaryl,C1-C20-haloalkyl, —SiR″₃, —OSiR″₃, —SR″, —PR″₂ or —NR″₂, each R″ isindependently a hydrogen or hydrocarbyl, e.g. C1-C20-alkyl,C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or C6-C20-aryl; ore.g. in case of —NR″₂, the two substituents R″ can form a ring, e.g.five- or six-membered ring, together with the nitrogen atom wherein theyare attached to;

R is a bridge of 1-7 atoms, e.g. a bridge of 1-4 C-atoms and 0-4heteroatoms, wherein the heteroatom(s) can be e.g. Si, Ge and/or Oatom(s), whereby each of the bridge atoms may bear independentlysubstituents, such as C1-C20-alkyl, tri(C1-C20-alkyl)silyl,tri(C1-C20-alkyl)siloxy or C6-C20-aryl substituents); or a bridge of1-3, e.g. one or two, hetero atoms, such as silicon, germanium and/oroxygen atom(s), e.g. —SiR¹ ₂—, wherein each R¹ is independentlyC1-C20-alkyl, C6-C20-aryl or tri(C1-C20-alkyl)silyl-residue, such astrimethylsilyl-;

M is a transition metal of Group 4 to 6, such as Group 4, e.g. Ti, Zr orHf,

each X is independently a sigma-ligand, such as H, halogen,C1-C20-alkyl, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl,C3-C12-cycloalkyl, C6-C20-aryl, C6-C20-aryloxy, C7-C20-arylalkyl,C7-C20-arylalkenyl, —SR″, —PR″₃, —SiR″₃, —OSiR″₃ or —NR″₂; each R″ isindependently hydrogen or hydrocarbyl, e.g. C1-C20-alkyl,C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or C6-C20-aryl; ore.g. in case of —NR″₂, the two substituents R″ can form a ring, e.g.five- or six-membered ring, together with the nitrogen atom wherein theyare attached to;

and each of the above mentioned ring moiety alone or as a part of amoiety as the substituent for Cp, X, R″ or R¹ can further be substitutede.g. with C1-C20-alkyl which may contain Si and/or O atoms;

n is 0, 1 or 2, e.g. 0 or 1,

m is 1, 2 or 3, e.g. 1 or 2,

q is 1, 2 or 3, e.g. 2 or 3,

wherein m+q is equal to the valency of M.

Said metallocenes II and their preparation are well known in the art.

Cp is preferably cyclopentadienyl, indenyl, tetrahydroindenyl orfluorenyl, optionally substituted as defined above and may further beara fused ring of 3 to 7 atoms, e.g. 4, 5 or 6, which ring may be aromaticor partially saturated.

In a suitable subgroup of the compounds of formula II, each Cpindependently bears one or more substituents selected from C1-C20-alkyl,C6-C20-aryl, C7-C20-arylalkyl (wherein the aryl ring alone or as a partof a further moiety may further be substituted as indicated above),—OSiR″₃, wherein R″ is as indicated above, preferably C1-C20-alkyl; X isas H, halogen, C1-C20-alkyl, C1-C20-alkoxy, C6-C20-aryl,C7-C20-arylalkenyl or —NR″₂ as defined above, e.g. —N(C1-C20-alkyl)₂; Ris a methylene, ethylene or a silyl bridge, whereby the silyl can besubstituted as defined above, e.g. a dimethylsilyl=,methylphenylsilyl=or trimethylsilylmethylsilyl=bridge; n is 0 or 1; m is2 and q is two.

Preferably, R″ is other than hydrogen.

A specific subgroup includes the well known metallocenes of Zr, Hf andTi with one or two, e.g. two, η⁵-ligands which may be bridged orunbridged cyclopentadienyl ligands optionally substituted with e.g.siloxy, alkyl and/or aryl as defined above, or with two unbridged orbridged indenyl ligands optionally substituted in any of the ringmoieties with e.g. siloxy, alkyl and/or aryl as defined above, e.g. at2-, 3-, 4- and/or 7-positions. As specific examples e.g.bis(alkylcyclopentadienyl)Zr (or Ti or Hf) dihalogenides can bementioned, such as bis(n-butylcyclopentadienyl)ZrCl₂ andbis(n-butylcyclopentadienyl)HfCl₂, see e.g. EP-A-129 368. Examples ofcompounds wherein the metal atom bears a —NR″₂ ligand are disclosed i.a.in WO-A-9856831 and WO-A-0034341. The contents of the above documentsare incorporated herein by reference. Further metallocenes are describede.g. in EP-A-260 130. As further examples of usable metallocenes mayalso be found e.g. from WO-A-9728170, WO-A-9846616, WO-A-9849208,WO-A-9912981, WO-A-9919335, WO-A-9856831, WO-A-00/34341, EP-A-423 101and EP-A-537 130 as well as V. C. Gibson et al., in Angew. Chem. Int.Ed., engl., vol 38, 1999, pp 428-447, the disclosures of which areincorporated herein by reference.

Alternatively, in a further subgroup of the metallocene compounds, themetal bears a Cp group as defined above and additionally a η¹ or η²ligand, wherein said ligands may or may not be bridged to each other.This subgroup includes so called “scorpionate compounds” (withconstrained geometry) in which the metal is complexed by a η⁵ ligandbridged to a η¹ or η² ligand, preferably η¹ (for example a σ-bonded)ligand, e.g. a metal complex of a Cp group as defined above, e.g. acyclopentadienyl group, which bears, via a bridge member, an acyclic orcyclic group containing at least one heteroatom, e.g. —NR″₂ as definedabove. Such compounds are described e.g. in WO-A-9613529, the contentsof which are incorporated herein by reference.

Any alkyl, alkenyl or alkynyl residue referred above alone or as a partof a moiety may be linear or branched, and contain preferably of up to9, e.g. of up to 6, carbon atoms. Aryl is preferably phenyl ornaphthalene. Halogen means F, Cl, Br or I, preferably Cl.

Another subgroup of the organotransition metal compounds of formula Iusable in the present invention is known as non-metallocenes wherein thetransition metal (preferably a Group 4 to 6 transition metal, suitablyTi, Zr or Hf) has a coordination ligand other than cyclopentadienylligand.

The term “non-metallocene” herein means compounds, which bear nocyclopentadienyl ligands or fused derivatives thereof, but one or morenon-cyclopentadienyl η- or σ-, mono-, bi- or multidentate ligand. Suchligands can be chosen e.g. from (a) acyclic, η¹ to η⁴- or η⁶-ligandscomposed of atoms from Groups 13 to 16 of the Periodic Table (IUPAC),e.g. an acyclic pentadienyl ligand wherein the chain consists of carbonatoms and optionally one or more heteroatoms from Groups 13 to 16(IUPAC), and in which the open chain ligand may be fused with one ortwo, preferably two, aromatic or non-aromatic rings and/or bear furthersubstituents (see e.g. WO 01 70395, WO 97 10248 and WO 99 41290), or (b)cyclic σ-, η¹- to η⁴- or η⁶-, mono-, bi- or multidentate ligandscomposed of unsubstituted or substituted mono-, bi- or multicyclic ringsystems, e.g. aromatic or non-aromatic or partially saturated ringsystems, containing carbon ring atoms and optionally one or moreheteroatoms selected from Groups 15 and 16 of the Periodic Table (IUPAC)(see e.g. WO 99 10353). Bi- or multidentate ring systems include alsobridged ring systems wherein each ring is linked via a bridging group,e.g. via an atom from Groups 15 or 16 of the Periodic Table, e.g. N, Oor S, to the transition metal atom (see e.g. WO 02 060963). As examplesof such compounds, i.a. transition metal complexes with nitrogen-based,cyclic or acyclic aliphatic or aromatic ligands, e.g. such as thosedescribed in the applicant's earlier application WO-A-9910353 or in theReview of V. C. Gibson at al., in Angew. Chem. Int. Ed., engl., vol 38,1999, pp 428-447 or with oxygen-based ligands, such as Group 4 metalcomplexes bearing bidentate cyclic or acyclic aliphatic or aromaticalkoxide ligands, e.g. optionally substituted, bridged bisphenolicligands (see i.a. the above review of Gibson et al.). Further specificexamples of non-η⁵ ligands are amides, amide-diphosphane, amidinato,aminopyridinate, benzamidinate, azacycloalkenyl, such astriazabicycloalkenyl, allyl, beta-diketimate and aryloxide. Thedisclosures of the above documents are incorporated herein by reference.It should be noted that the diversity does not affect the applicabilityof the process of the invention, whose essential particle-shapingmeasures remain unaffected by the particular content of the particles tobe shaped.

The preparation of metallocenes and non-metallocenes, and the organicligands thereof, usable in the invention is well documented in the priorart, and reference is made e.g. to the above cited documents. Some ofsaid compounds are also commercially available. Thus, said transitionmetal compounds can be prepared according to or analogously to themethods described in the literature, e.g. by first preparing the organicligand moiety and then metallating said organic ligand (η-ligand) with atransition metal. Alternatively, a metal ion of an existing metallocenecan be exchanged for another metal ion through transmetallation.

If several different transition metal compounds are used (mixed dual ormulticatalyst systems), these can be any combinations of the aboveorganometal compounds or of the above organometal compounds with othercatalyst compounds (including Ziegler-Natta and chromium oxide systems),e.g. a combination at least of two or more a metallocenes, of ametallocene and a non-metallocene, as well as of a metallocene and/or anon-metallocene with a Ziegler-Natta catalyst system (which comprises atransition metal compound and a compound of a metal from Group 2 of thePeriodic Table, such as a Mg compound).

As stated above, the catalyst prepared according to the presentinvention may further comprise one or more cocatalysts well known in theart, preferably an activator containing aluminium or boron. Examples ofsuch activators are organo aluminium compounds, such astrialkylaluminium compound and/or aluminoxane compound, ornon-coordination ionic cocatalysts, such as boron activators.

Preferred as cocatalysts for metallocenes and non-metallocenes, ifdesired, are the aluminoxanes, in particular theC1-C10-alkylaluminoxanes, most particularly methylaluminoxane (MAO).Such aluminoxanes can be used as the sole cocatalyst or together withother cocatalyst(s). Thus besides or in addition to aluminoxanes, othercation complex forming catalysts activators can be used. In this regardmention may be made particularly to boron compounds known in the art.Said activators are commercially available or can be prepared accordingto the prior art literature.

Further aluminoxane cocatalysts are described i.a. in WO-A-9428034 whichis incorporated herein by reference. These are linear or cyclicoligomers of having up to 40, preferably 3 to 20, -(Al(R′″)O)— repeatunits (wherein R′″ is hydrogen, C1-C10-alkyl (preferably methyl) orC6-C18-aryl or mixtures thereof).

The use and amounts of the such activators are within the skills of anexpert in the field. As an example, with the boron activators, 5:1 to1:5, preferably 2:1 to 1:2, such as 1:1, ratio of the transition metalto boron activator may be used. In case of aluminoxanes, such asmethylaluminumoxane (MAO), the amount of Al, provided by aluminoxane,can be chosen to provide an Al:transition metal molar ratio e.g. in therange of 1:1 to 10 000:1, suitably 5:1 to 8000:1, preferably 10:1 to7000:1, e.g. 100:1 to 4000:1, as normally used for homogeneous catalystsystems, or, depending on the used catalyst froming compounds, also 10:1to 500:1, such as 100:1 to 300:1 as normally used for heterogeneouscatalyst systems may be used.

The quantity of cocatalyst to be employed in the catalyst of theinvention is thus variable, and depends on the conditions and theparticular transition metal compound chosen in a manner well known to aperson skilled in the art.

Any additional components to be contained in the solution comprising theorganotransition compound may be added to said solution before or,alternatively, after the dispersing step.

Solidification Step

As stated above the immobilising/solidifying may be effected in manyways: One of the preferred embodiments is by polymerisation of anolefinic monomer present in said droplets. The olefinic monomer canconveniently be an alkene employed as solvent to form the solution ofthe catalyst component(s).

In a further embodiment of the invention prepolymerisation is effectedby adding a monomer, in liquid or, preferably, in gaseous state to theemulsion. A catalytically active transition metal component or any othercatalytically active compound, such as a peroxide, present in thedroplets of the solution causes the monomers to polymerise within thedroplets. The formed polymer matrix in turn causes the droplets tosolidify. It is also possible to use a combination of the liquid andgaseous monomer(s) which may contain the same or different monomer.

The amount of monomer used may correspond to the amount of the solution.

The monomer used for prepolymerising the droplets of the at least twophase system can be any conventional gaseous or liquid monomer. When thesolvent used to form the solution of the catalyst component(s) is notthe solidifying monomer, a gaseous monomer is preferably used. Asexamples, olefin monomers each having 2 to 20 carbon atoms can be used.The olefin can be linear or branched, cyclic or acyclic, aromatic oraliphatic, including ethylene, propylene, 1-butene, 1-pentene,2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene,2,3-dimethyl-1-butene, 1-octene, styrene, vinylcyclohexane etc.

The monomer used for the prepolymerisation can be the same or different,preferably the same, to that used for the actual polymerisation step;also a comonomer can be used in the prepolymerisation step. Theprepolymerisation conditions (temperature, time period etc.) can bechosen analogously to those described in the art, and will obviouslyavoid any risk of breaking the emulsion which defines the droplets. Incase a liquid monomer is used as solution for the catalyst components,the actual prepolymerisation reaction/immobilisation step can beinitiated and controlled e.g. by the temperature.

In general the monomer is used in amounts sufficient to cause theprecipitation of the formed prepolymer, i.e. the formation of a solidprepolymer matrix, within the droplets, whereby solid polymericparticles with uniform size are obtained containing the catalystcomponent(s) fixed to the matrix. The size of the formed particles canbe controlled by the droplet size of the dispersed phase, the catalystconcentration in the solution, the used amount of the monomer and/or theprepolymerisation conditions (time, temperature etc).

The principles of prepolymerisation as described e.g. in EP-A-279 863,the contents of which are incorporated herein by a reference, can beused. Furthermore, in general, e.g. a gaseous monomer feed may bediluted with nitrogen or other inert gas. Also a hydrogen can be used ina known manner during the prepolymerisation to control molecular weightof the prepolymer.

Alternatively, the solidifying may be effected by inducing within thedroplets a chemical reaction between two or more reactants which yieldsa solid product containing the catalyst. The induction can be achievedby adding a reactant(s) and/or by changing the temperature. Moreover thesolidification may be effected by cross-linking said activator with across-linking agent. E.g. the cross-linking of an aluminoxane, such asMAO, can be effected in a known manner using the principles describede.g. EP-A-685 494, the contents of which are incorporated herein byreference.

In a particularly preferred embodiment, the solidification is effectedafter the emulsion system is formed by subjecting the system to anexternal stimulus, such as a temperature change. Temperature differencesof e.g. 5 to 100° C., such as 10 to 100° C., or 20 to 90° C., such as 50to 80° C., e.g. 70 to 80° C. can be used.

The emulsion system may be subjected to a rapid temperature change tocause a fast solidification in the dispersed system. The dispersed phasemay e.g. be subjected to an immediate (within milliseconds to fewseconds) temperature change in order to achieve an instantsolidification of the component(s) within the droplets. The appropriatetemperature change, i.e. an increase or a decrease in the temperature ofan emulsion system, required for the desired solidification rate of thecomponents cannot be limited to any specific range, but naturallydepends on the emulsion system, i.a. on the used compounds and theconcentrations/ratios thereof, as well as on the used solvents, and ischosen accordingly. It is also evident that any techniques may be usedto provide sufficient heating or cooling effect to the dispersed systemto cause the desired solidification.

In one embodiment the heating or cooling effect is obtained by bringingthe emulsion system with a certain temperature to an inert receivingmedium with significantly different temperature, e.g. as stated above,whereby said temperature change of the emulsion system is sufficient tocause the rapid solidification of the droplets. The receiving medium canbe gaseous, e.g. air, or a liquid, preferably a solvent, or a mixture oftwo or more solvents, wherein the catalyst component(s) is(are)immiscible and which is inert in relation to the catalyst component(s).For instance, the receiving medium comprises the same immiscible solventused as the continuous phase in the first emulsion formation step. Saidsolvents can be used alone or as a mixture with other solvents, such asaliphatic or aromatic hydrocarbons, such as alkanes. Preferably afluorinated solvent as the receiving medium is used, which may be thesame as the continuous phase in the emulsion formation, e.g.perfluorinated hydrocarbon. Alternatively, the temperature differencemay be effected by gradual heating of the emulsion system, e.g. up to10° C. per minute, preferably 0.5 to 6° C. per minute and morepreferably in 1 to 5° C. per minute.

In case a melt of e.g. a hydrocarbon solvent is used for forming thedispersed phase, the solidifcation of the droplets may be effected bycooling the system using the temperature difference stated above.

Preferably, the “one phase” change as usable for forming an emulsion canalso be utilised for solidifying the catalytically active contentswithin the droplets of an emulsion system by, again, effecting atemperature change in the dispersed system, whereby the solvent used inthe droplets becomes miscible with the continuous phase, preferably afluorous continuous phase as defined above, so that the droplets becomeimpoverished of the solvent and the solidifying components remaining inthe “droplets” start to solidify. Thus the immisciblity can be adjustedwith respect to the solvents and conditions (temperature) to control thesolidification step.

The miscibility of e.g. fluorous solvents with organic solvents can befound from the literature and be chosen accordingly by a skilled person.Also the critical temperatures needed for the phase change are availablefrom the literature or can be determined using methods known in the art,e.g. the Hildebrand-Scatchard-Theorie. Reference is also made to thearticles of A. Enders and G. and of Pierandrea Lo Nostro cited above.

Thus according to the invention, the entire or only part of the dropletmay be converted to a solid form. The size of the “solidified” dropletmay be smaller or greater than that of the original droplet, e.g. if theamount of the monomer used for the prepolymerisation is relativelylarge.

The solid catalyst particles recovered can be used, after an optionalwashing step, in a polymerisation process of an olefin. Alternatively,the separated and optionally washed solid particles can be dried toremove any solvent present in the particles before use in thepolymerisation step. The separation and optional washing steps can beeffected in a known manner, e.g. by filtration and subsequent washing ofthe solids with a suitable solvent.

The solid particles obtained may have an average size range of 1 to 500μm, particularly 5 to 500 μm, advantageously 5 to 200 μm, e.g. 10 to 100μm, or even 5 to 50 μm, all sizes of which may be usable, depending onthe polymerisation the catalyst is used for. As stated above, the sizecan be determined i.a. by the amount of the immobilising agent, e.g.monomer, used in the method.

The present method enables to prepare catalyst particles with highcatalytic activity. Preferably, the present catalyst particles have alsovery low porosity and a low surface area, e.g. of less than 50 m²/g,preferably less than 30 m²/g and more preferably less than 20 m²/g.

Polymerisation Process

The catalyst system of the invention can then be used alone or togetherwith an additional cocatalyst(s) in the actual polymerisation step in amanner known in the art.

The olefin to be polymerised using the catalyst system of the inventioncan be any olefin polymerisable in a coordination polymerisationincluding an alpha-olefin alone or as a mixture with one or morecomonomers. Preferable olefins are ethylene or propene, or a mixture ofethylene or propene with one or more alpha-olefin(s). Preferablecomonomers are C2-C12-olefins, preferably C4-C10-olefins, such as1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,1-octene, 1-nonene, 1-decene, as well as diene, such as butadiene,1,7-octadiene and 1,4-hexadiene, or cyclic olefins, such as norbornene,and any mixtures thereof.

Polyethene and any copolymers thereof are particularly contemplated, asare polypropylene homopolymers and any copolymers thereof.

Furthermore, the catalyst system of the invention can be used for thepolymerisation of long chain branched alpha-olefins (with 4 to 40 Catoms), alone or together with short chain branched alpha-olefins.

Polymerisation may be effected in one or more, e.g. one, two or threepolymerisation reactors, using conventional polymerisation techniques,in particular gas phase, solution phase, slurry or bulk polymerisation.Polymerisation can be a batch or continuous polymerisation process.Generally a combination of slurry (or bulk) and at least one gas phasereactor is preferred, particularly with gas phase operation coming last.

For slurry reactors, the reaction temperature will generally be in therange of 60 to 110° C. (e.g. 85-110° C.), the reactor pressure willgenerally be in the range 5 to 80 bar (e.g. 50-60 bar), and theresidence time will generally be in the range 0.3 to 5 hours (e.g. 0.5to 2 hours). The diluent used will generally be an aliphatic hydrocarbonhaving a boiling point in the range −70 to +100° C. In such reactors,polymerisation may, if desired, be effected under supercriticalconditions.

For gas phase reactors, the reaction temperature used will generally bein the range 60 to 115° C. (e.g. 70 to 110° C.), the reactor pressurewill generally be in the range 10 to 25 bar, and the residence time willgenerally be 1 to 8 hours. The gas used will commonly be a non-reactivegas such as nitrogen or propane together with monomer (e.g. ethylene orpropylene).

Generally the quantity of catalyst used will depend upon the nature ofthe catalyst, the reactor types and conditions and the propertiesdesired for the polymer product. Conventional catalyst quantities, suchas described in the publications referred herein, may be used.

With the method of the invention a catalyst system with a high bulkdensity and a good morphology is obtained and the catalyst exhibits ahigh catalytic activity. The bulk density and morphology correlate withproduct bulk density and morphology—the so-called “replica effect”. Thusthe catalyst leads to a polymer with a higher bulk density than obtainedwith homogeneous systems of the prior art, without using an externalsupport material. Accordingly, the catalyst of the method of theinvention combines the advantages of the prior art homogeneous andheterogeneous catalyst systems.

EXAMPLES

The following examples are provided by way of illustration of theinvention. The starting materials, reagents and solvents used arecommerically available, or can be prepared according to or analogouslyto the methods described in the prior art literature.

Example 1 Complex Preparation

49.3 mg of bis(n-butyl-cyclopentadienyl)zirconium dichloride (Eurocen5031, Witco GmbH) were reacted with 4 ml MAO solution, 30 wt-% intoluene (Albemarle) under stirring at room temperature in a septa bottlefor 30 minutes. A yellow solution of activated complex (with targetAl/Zr=200) was obtained.

Surfactant Preparation

284 mg of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol (ApolloScientific, UK) were added slowly to 0.5 ml MAO under stirring. A heavyreaction with liberation of gas occurs. Afterwards, additional 0.5 ml ofMAO were added to the solution. No visible reaction was observed.

Emulsion Formation

20 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) werebubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into a 50 ml glass reactor with four baffles and an anchor-typestirrer. The above-mentioned activated complex solution and theabove-mentioned surfactant were added successively. A liquid-liquidtwo-phase system was formed. The mixture was stirred for 10 minutes with500 rpm under cooling in an ice bath. A milky emulsion was formed.

Solidification

60 ml of dried perfluorooctane (P & M Invest, Moscow, Russia) werebubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into a 200 ml glass reactor equipped with an anchor-type stirrer.The reactor is heated up to 90° C. in an oil bath and stirred with 300rpm. Then the above-mentioned emulsion is transferred via an teflon tubeand (nitrogen-) overpressure into the hot perfluorooctane. Solidparticles are formed immediately.

Isolation

The stirring is ceased, and the reactor cooled down. The liquid issiphoned out of the reactor, and the remaining catalyst is dried for onehour at 50° C. in a nitrogen flow. Then the reactor is introduced intothe glove box and the dried catalyst is taken out and weighted.

Catalyst Characterization

The catalyst composition is analyzed via elementary analysis, theAl-content is 27.8 wt-%, the Zr-content is 0.42 wt-%. The averageparticle diameter (analyzed via Coulter counter) is 22 μm. The particlesize distribution is shown in FIG. 1.

The specific surface of the catalyst, analyzed via nitrogen-adsorption(BET-method) is 14 m²/g. The catalyst particles have a nearly perfectspherical shape as shown in FIG. 2.

Test Polymerization

The polymerizations were performed in a 3 l stainless steel autoclavereactor equipped with a paddle stirrer. 1 l dried and deoxygenatedi-butane used as medium was charged to the reactor, which was beforehanddried at +100° C. in vacuum and then purged with nitrogen. 16.6 mg ofcatalyst was weighed into a metal cylinder in the glove box. Then thecatalyst cylinder was connected to the reactor and the catalyst wasadded to the reactor with 0,8 l i-butane (Messer Griesheim). The reactorwas heated up to +80° C. and then ethylene (Borealis polymerisationgrade) was introduced to the reactor. The total pressure was adjusted tohave 5 bar ethylene partial pressure in the reactor. Continuous flow ofethylene kept the total pressure constant. Comonomer (40 ml of 1-hexene,Borealis polymerisation grade) was fed to the reactor simultaneouslywith ethylene. The polymerization was continued for 60 min and afterthat the polymerization was stopped.

The formed polymer was weighted and the activity was calculated to be9.04 kg PE/g cat./h.

Example 2 Complex Preparation

40.8 mg of bis(n-butylcyclopentadienyl)zirconium dichloride

(Eurocen 5031, Witco GmbH) was reacted with 4 ml MAO (30 wt-% intoluene, Albemarle) under stirring at room temperature in a septabottlefor 30 minutes. A yellow solution of activated complex (with targetAl/Zr=200) was obtained.

Surfactant Preparation

195 mg of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1-nonanol(Apollo Scientific, UK) was added slowly to 0.5 ml MAO under stirring. Aheavy reaction with liberation of gas occurred. Afterwards, additional0.5 ml of MAO was added to the solution. No visible reaction wasobserved.

Emulsion Formation

20 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) wasbubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into 50 ml glass reactor with four baffles and an anchor-typestirrer. The above-mentioned activated complex solution and theabove-mentioned surfactant are added successively. A liquid-liquidtwo-phase system is formed. The mixture is stirred for 10 minutes with500 rpm under cooling in an ice bath. A milky emulsion is formed.

Solidification

60 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) wasbubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into 200 ml glass reactor with four an anchor-type stirrer. Thereactor was heated up to 90° C. in an oil bath and stirred with 300 rpm.Then the above-mentioned emulsion was transferred via a teflon tube and(nitrogen-) overpressure into the hot perfluorooctane. Solid particleswere formed immediately.

Isolation

The stirring is ceased and the reactor cooled down. The liquid wassiphoned out of the reactor and the remaining catalyst is dried for onehour at 50° C. in a nitrogen flow. Then the reactor was taken out andweighted.

Example 3 Complex Preparation

42.9 mg of bis(n-butylcyclopentadienyl)zirconium dichloride (Eurocen5031, Witco GmbH) was reacted with 4 ml MAO (30 wt-% in toluene,Albemarle) under stirring at room temperature in a septabottle for 30minutes. A yellow solution of activated complex (with target Al/Zr=200)was obtained.

Surfactant Preparation

168 mg of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol (ApolloScientific, UK) was added slowly to 0.5 ml MAO under stirring. A heavyreaction with liberation of gas occurred. Afterwards, additional 0.5 mlof MAO was added to the solution. No visible reaction was observed.

Emulsion Formation

20 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) wasbubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into 50 ml glass reactor with four baffles and an anchor-typestirrer. The above-mentioned activated complex solution and theabove-mentioned surfactant are added successively. A liquid-liquidtwo-phase system is formed. The mixture is stirred for 10 minutes with500 rpm under cooling in an ice bath. A milky emulsion is formed.

Solidification

60 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) wasbubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into 200 ml glass reactor with four an anchor-type stirrer. Thereactor was heated up to 50° C. in an oil bath and stirred with 300 rpm.Then the above-mentioned emulsion was transferred via a teflon tube and(nitrogen-) overpressure into the hot perfluorooctane. Solid particleswere formed immediately.

Example 4 Complex Preparation

80.3 mg of bis(n-butylcyclopentadienyl)hafnium dichloride (TA02823,Witco GmbH) was reacted with 4 ml MAO (30 wt-% in toluene, Albemarle)under stirring at room temperature in a septabottle for 30 minutes. Ayellow solution of activated complex (with target Al/Hf-200) wasobtained.

Surfactant Preparation

455 mg of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol (ApolloScientific, UK) was added slowly to 1.0 ml MAO under stirring. A heavyreaction with liberation of gas occurred. Afterwards, additional 1.0 mlof MAO was added to the solution. No visible reaction was observed.

Emulsion Formation

20 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) wasbubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into 50 ml glass reactor with four baffles and an anchor-typestirrer. The above-mentioned activated complex solution and theabove-mentioned surfactant are added successively. A liquid-liquidtwo-phase system is formed. The mixture is stirred for 10 minutes with500 rpm under cooling in an ice bath. A milky emulsion is formed.

Solidification

60 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia) wasbubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into 200 ml glass reactor with four an anchor-type stirrer. Thereactor was heated up to 50° C. in an oil bath and stirred with 300 rpm.Then the above-mentioned emulsion was transferred via a teflon tube and(nitrogen-) overpressure into the hot perfluorooctane. Solid particleswere formed immediately.

Example 5 Complex Preparation

54.2 mg of rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂ (CATALYTICA ADVANCEDTECHNOLOGIES) were reacted with 4 ml MAO solution, 30%-wt. in toluene(Albemarle) under stirring at room temperature in a septa bottle for 30minutes. A yellow solution of activated complex with (target Al/Zr=250)was obtained.

Surfactant Preparation

0.1 ml of 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptanol

(Appollo Scientific, UK) were added slowly to 0.5 ml MAO under stirring.A heavy reaction with liberation of gas occurs. Afterwards, additional0.5 ml of MAO were added to the solution. No visible reaction wasobserved.

Emulsion Formation

20 ml of dried perfluorooctane (98%, P & M Invest, Moscow, Russia), werebubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into a 50 ml glass reactor with four baffles and an anchor-typestirrer. The under 1) described activated complex solution and the under2) described surfactant are added successively. A liquid-liquidtwo-phase systems is formed. The mixture is stirred for 10 minutes with500 rpm under cooling in an ice bath. A milky emulsion is formed.

Solidification

60 ml of dried perfluorooctane (P & M Invest, Moscow, Russia), werebubbled with nitrogen for 15 minutes (to remove oxygen traces) andfilled into a 200 ml glass reactor equipped with an anchor-type stirrer.The reactor is heated up to 90° C. in an oil bath and stirred with 300rpm. Then the under 3) formed emulsion is transferred via an Teflon tubeand (nitrogen-) overpressure into the hot perfluorooctane. Solidparticles are formed immediately.

Isolation

The stirring is ceased, and the reactor cooled down. The liquid issiphoned out of the reactor, and the remaining catalyst is dried for onehour at 50° C. in a nitrogen flow. Then the reactor is introduced intothe glove box and the dried catalyst is taken out and weighted.

Catalyst Characterisation

The catalyst composition is analyzed via elementary analysis, theAl-content is 35%-wt., the Zr-content is 0.7%-wt. The average particlediameter (analyzed via Coulter counter) is 22 μm. The particle sizedistribution is shown in FIG. 3. The complex can preferably be used forthe polymerisation of propene.

Example 6 Complex Preparation

The catalyst according to example 5 is prepared, except thatrac-Me₂Si(2-Me-4-PhInd)₂ZrClN(Et₂) is used as the complex.

Starting Material

ZrCl₄ (available from Strem Chemicals) is reacted with LiN(Et)₂(available from Aldrich, or can be prepared according to Houben-Weyl“Methoden der Organischen Chemie”, Bd. 13/1, 99 Thieme, Stuttgart, 1970)in a molar ratio of ZrCl₄:LiN(Et)₂ of 1:4, resp., to prepareZr(N(Et)₂)₄. The reaction is effected analogously to the proceduredescribed in D. C. Bradley, I. M. Thomas Can. J. Chem. 40, 1962, 449-454and D. C. Bradley, I. M. Thomas J. Chem. Soc., 1960, 3857.

The obtained Zr(N(Et)₂)₄ is allowed to react with ZrCl₄ (in a molarratio of 1:3) to obtain Cl₃ZrN(Et₂) (procedure analogously to methoddescribed in M. F. Lappert, G. Chandra J. Chem. Soc. A, 1968,1940-1945).

Dimethylsilyl-bis(2-methyl-4-phenyl)indene (1) (available fromCatalytica, or can be prepared according to procedure described i.a. inEP 790 076, Example A, steps 1-4).

Complex Formation

The Li-salt (2) of the ligand (1) was made analogously to the basicprocedure descirbed i.a. in EP 790 076 (see also W. A. Herrmann, J.Rohrmann, E. Herdtweck, W. Spaleck, A. Winter Angew. Chem. 101, 1989,1536 and Angew. Chem. Int. Ed. 28, 1989, 1511).

The reaction of the obtained Li-salt (2) with C13NEt2 was done twice: 1)at room temp in THF and 2) at −70 C in Et2O. In the first case arac:meso mixture of product (3) ca. 54.5% 45.5% was obtained. In thesecond case, the corresponding ratio was 92%:8%. The rac-form can beseparated in a conventional manner, e.g. by recrystallisation fromdiethylether.

Complex Characterisation

1H-NMR (270 MHz, THF-d8): 8.0-6.8 (m, 18H, arom. H), 3.00 (m, 2H, NCH2),2.70 (m, 2H, NCH2), 2.57 (s, 3H, CH3), 2.31 (s, 3H, CH3), 1.33 (s, 3H,Si—CH3), 1.22 (s, 3H, Si—CH3), 0.50 (t, 6H, 2×CH3).

1.-41. (canceled)
 42. A solid catalyst comprising an organometalliccompound of a transition metal of Group 3 to 10 of the Periodic Tableobtainable according to a process comprising preparing a homogeneoussolution of one or more catalyst components; dispersing said solution ina solvent immiscible therewith to form a liquid/liquid emulsion systemin which said one or more catalyst components are present in thedroplets of the dispersed phase; solidifying said dispersed phase toconvert said droplets to solid particles, wherein the solidification iseffected within the droplets.
 43. A solid catalyst comprising anorganometallic compound of a transition metal of Group 3 to 10 of thePeriodic Table and exhibiting a high catalytic activity comprising: aspherical shape; a uniform distribution of the chemical composition ofthe catalyst both intra and inter particles; a predetermined particlesize range of 1-500 μm; and a low surface area of less than 50 m²/gmeasured by the BET-method.
 44. The catalyst according to claim 42,wherein said solvent is an organic solvent or a mixture thereof.
 45. Thecatalyst according to claim 44, wherein said solvent is a linear,branched, or cyclic alkane or alkene, an aromatic hydrocarbon and/or ahalogen-containing hydrocarbon, or a mixture thereof.
 46. The catalystaccording to claim 42, wherein said immiscible solvent which forms thecontinuous phase is an inert solvent or a mixture thereof, which doesnot undergo chemical reactions with any catalyst forming component orprecursor thereof.
 47. The catalyst according to claim 42, wherein saidimmiscible solvent which forms the continuous phase comprises afluorinated organic solvent, a functionalized derivative thereof, or amixture thereof.
 48. The catalyst according to claim 42, wherein saidimmiscible solvent which forms the continuous phase comprises afluorinated hydrocarbon, a functionalized derivative thereof, or amixture thereof.
 49. The catalyst according to claim 42, wherein saidimmiscible solvent comprises a semi-, highly, or perfluorinatedhydrocarbon, a functionalized derivative thereof, or a mixture thereof.50. The catalyst according to claim 49, wherein said immiscible solventcomprises a C3-C30 perfluoroalkane, -alkene, or -cycloalkane, or amixture thereof.
 51. The catalyst according to claim 49, wherein saidimmiscible solvent comprises a perfluorohexane, perfluoroheptane,perfluorooctane, or perfluoro (methylcyclohexane), or a mixture thereof.52. The catalyst according to claim 49, wherein said immiscible solventcomprises a perfluorohydrocarbon or a functionalized derivative thereofor a mixture thereof.
 53. The catalyst according to claim 42 or 43,wherein said catalyst further comprises an activator containing aluminumor boron as said catalyst component.
 54. The catalyst according to claim42, wherein said catalyst is formed in situ from catalyst components insaid solution.
 55. The catalyst according to claim 42, wherein anemulsifying agent is present during the formation of said emulsion. 56.The catalyst according to claim 55, wherein said emulsifying agent isprepared by reacting a surfactant precursor bearing at least onefunctional group, with a compound reactive with said functional group inthe catalyst solution or in the solvent forming the continuous phasebefore the addition of the organometallic compound of the transitionmetal of Group 3 to 10 of the Periodic Table (IUPAC) or of an actinideor lanthanide.
 57. The catalyst according to claim 55, wherein saidemulsifying agent is prepared by reacting a highly fluorinatedC₁₋₃₀-alcohol surfactant precursor with a cocatalyst compound.
 58. Thecatalyst according to claim 57, wherein said surfactant precursor is ahighly fluorinated C₄₋₂₀-alcohol.
 59. The catalyst according to claim57, wherein said surfactant precursor is a highly fluorinatedC₅₋₁₀-alcohol.
 60. The catalyst according to claim 42, wherein thesolidification is effected by a temperature change treatment.
 61. Thecatalyst according to claim 60, wherein said temperature changetreatment comprises subjecting the emulsion to gradual temperaturechange of up to 10° C. per minute.
 62. The catalyst according to claim60, wherein said temperature change treatment comprises subjecting theemulsion to gradual temperature change of up to 0.5 to 6 per minute. 63.The catalyst according to claim 60, wherein said temperature changetreatment comprises subjecting the emulsion to gradual temperaturechange of up to 1 to 5° C. per minute.
 64. The catalyst according toclaim 60, wherein said temperature change treatment comprises subjectingthe emulsion to a temperature change of more than 40° C. within lessthan 10 seconds.
 65. The catalyst according to claim 60, wherein saidtemperature change treatment comprises subjecting the emulsion to atemperature change of more than 50° C. within less than 6 seconds. 66.The catalyst according to claim 42, wherein the liquid/liquid emulsionsystem of droplets, which comprises said solution of the homogeneouscatalyst, further comprises an olefinic monomer, and the solidificationof the dispersed droplets is effected by polymerizing of an olefinicmonomer.
 67. The catalyst according to claim 66, wherein an olefinicmonomer is employed as solvent to form said solution.
 68. The catalystaccording to claim 66, wherein the olefinic monomer is a gas and isadded to the emulsion system to effect the prepolymerization of saidmonomer in the dispersed droplets.
 69. The catalyst according to claim42, wherein the liquid/liquid emulsion system of droplets, whichcomprises said solution of the homogeneous catalyst, further comprisescross-linking agent and an activator and the solidification of thedispersed droplets to form solid particles is effected by cross-linkingthe activator with the cross-linking agent.
 70. The catalyst accordingto claim 42 or 43, wherein the transition metal compound is of Group 4to 6 of the Periodic Table (IUPAC).
 71. The catalyst according to claim42 or 43, wherein the transition metal compound is a compound of formula(I):(L)_(m)R_(n)MX_(q)  (I) wherein N is a transition metal as defined inclaim 1 or claim 25 and each X is independently a σ-ligand, each L isindependently an organic ligand which coordinates to M, R is a bridginggroup linking two ligands L, m is 1, 2 or 3; n is 0 or 1; q is 1, 2 or3; and m+q is equal to the valency of the metal.
 72. The catalystaccording to claim 71, wherein the organometallic compound of atransition metal is a metallocene.
 73. The catalyst according to claim71, wherein the organometallic compound of a transition metal is anon-metallocene.
 74. The catalyst according to claim 42, wherein thesolid catalyst particles are recovered and subjected to washing anddrying.
 75. The catalyst according to claim 42 or 43, wherein therecovered particles have an average size range of 5 to 200 μm.
 76. Thecatalyst according to claim 75, wherein the recovered particles have anaverage size range of 10 to 100 μm.
 77. The catalyst according to claim42 wherein the solid particles having a spherical shape, a predeterminedparticle size distribution, and a surface area of less than 50 m²/g. 78.The catalyst of claim 42 or 43, wherein said particles have a surfacearea of less than 30 m²/g.
 79. The catalyst of claim 42 or 43, whereinsaid particles have a surface area of less than 20 m²/g.
 80. A method ofhomo- or copolymerizing olefins comprising comprising contacting thecatalyst according to claim 42 or 43 said olefins.
 81. The methodaccording to claim 80, wherein said olefins are C₂ to C₁₀ α-olefins. 82.The method according to claim 80, wherein said olefins are C₂ to C₁₀propene or ethene α-olefines, or copolymers thereof.
 83. A polyolefinwhich is obtainable using the catalyst of claim 42 or 43.